Polymerization catalyst and process

ABSTRACT

A catalyst is provided for addition polymerization of olefinically unsaturated monomers comprising a first compound MY, wherein M is a transition metal in a low valency state or a transition metal in a low valency state coordinated to at least one coordinating non-charged ligand, Y is a monovalent, divalent or polyvalent counterion; an initiator compound comprising a homolytically breakable bond with a halogen atom; and an organodiimine, where at least one of the nitrogens of the diimine is not part of an aromatic ring. A catalyst for addition polymerization of olefinically unsaturated monomers is also provided comprising a first component of Formula 
     
       
         [ML] n+  A n− , 
       
     
     wherein M=a transition metal of low valency state, L=an organodiimine where at least one of the nitrogens of the diimine is not part of an aromatic ring, A=an anion, n=an integer of 1 to 3, m=an integer of 1 or 2; 
     e) An initiator compound comprising a homolytically breakable bond with a halogen atom. 
     Preferably, the organodiimine is a 1,4-diaza-1,3-butadiene, a pyridine carbaldelyde imine, an oxazolidone or a quinoline carbaldehyde. 
     Processes for using the catalysts are also disclosed.

BACKGROUND OF THE INVENTION

1. Field of Invention

The present invention relates to a process for the atom transferpolymerization of olefinically unsaturated monomers in which molecularweight control is achieved by the presence of certain transition metals,especially copper, and diimine complexes.

2. Description of Related Art

It is desirable to be able to produce high molecular weight polymerswith a low molecular weight distribution by catalyzed additionpolymerization, in particular of vinylic monomers. Hitherto, this hasbeen achieved by polymerizing via ionic processes typically in thepresence of organometallics such as alkyl lithiums that are sensitivewhen reacted with water and other protic species. Therefore, monomerscontaining functional groups are not readily polymerized. The use ofionic systems also precludes the use of solvents that contain proticgroups and/or impurities resulting in very stringent reaction conditionsand reagent purity being employed.

More recently, radical polymerization systems based on the combinationof a transition metal halide and an alkyl halide have been used. Forexample, Matyjasewski (Macromolecules (1995), vol. 28, pages 7901-7910and W096/30421) describes the use of CuX (where X=Cl, Br) in conjunctionwith bipyridine and an alkyl halide to give polymers of narrow molecularweight distribution and controlled molecular weight. This system suffersfrom the disadvantage that the copper catalyst is only partially solublein the system and thus a heterogeneous polymerization ensues. The levelof catalyst that is active in solution is thus difficult to determine.Percec (Macromolecules, (1995), vol. 28, page 1995) has extendedMatyjasewski's work by using arenesulphonyl chlorides to replace alkylchlorides, again this results in heterogeneous polymerization. Sawamoto(Macromolecules, (1995), vol. 28, page 1721 and Macromolecules, (1997),vol. 30, page 2244) has also used a ruthenium based system for similarpolymerization of methacrylates. This system requires activation ofmonomer by aluminum alkyl, itself sensitive to reaction with proticspecies which is an inherent disadvantage. These systems have beendescribed as proceeding via a free radical mechanism that suffers fromthe problem that the rate of termination is >0 due to normalradical-radical combination and disproportionation.

SUMMARY OF THE INVENTION

Surprisingly, the inventors of the present invention have found that theuse of diimines such as 1,4-diaza-1,3-butadienes and2-pyridinecarbaldehyde imines may be used in place of bipyridines. Theseligands offer the advantage of homogeneous polymerization and thus thelevel of active catalyst can be accurately controlled. This class ofligand also enables the control of the relative stability of thetransition metal valencies, for example, Cu(I) and Cu(II), by alteringancillary substituents and thus gives control over the nature of theproducts through control over the appropriate chemical equilibrium. Sucha system is tolerant to trace impurities, trace levels of O₂ andfunctional monomers, and may even be conducted in aqueous media.

A further advantage of the system of the present invention is that thepresence of free-radical inhibitors traditionally used to inhibitpolymerization of commercial monomers in storage, such as 2,6-di-tert-butyl-4-methylphenol (topanol), increases the rate of reactionof the present invention. This means that lengthy purification ofcommercial monomers to remove such radical inhibitors is not required.Furthermore, this indicates that the system of the invention is not afree-radical process. This is contrary to the Matajaszewski and Sawamotowho show free-radical based systems.

Accordingly a first aspect of the invention provides a catalyst foraddition polymerization of olefinically unsaturated monomers, especiallyvinylic monomers, comprising:

a) a first compound of formula 1

MY

 where M is a transition metal in a low valency state or a transitionmetal in a low valency state coordinated to at least one coordinatingnon-charged ligand and Y is a monovalent or polyvalent counterion;

b) an initiator compound comprising a homolytically cleavable bond witha halogen atom.

A “homolytically cleavable bond” means a bond that breaks withoutintegral charge formation on either atom by homolytic fissionConventionally, this produces a radical on the compound and a halogenatom radical. For example:

However, the increase in the rate of reaction observed by the inventorswith free-radical inhibitors indicates that true free-radicals do notappear to be formed using the catalysts of the present invention. It isbelieved that this occurs in a concerted fashion whereby the monomer isinserted into the bond without formation of a discrete free radicalspecies in the system. That is, during propagation this results in theformation of a new carbon-carbon bond and a new carbon-halogen bondwithout free-radical formation. The mechanism involves bridging halogenatoms such as:

where:

 ML is a transition metal-diimine complex as defined below. A“free-radical” is defined as an atom or group of atoms having anunpaired valence electron and which is a separate entity without otherinteractions.

c) an organodiimine, where one of the nitrogens of the diimine is notpart of an aromatic ring.

Transitional metals may have different valencies, for example Fe(II) andFe(III), Cu(I) and Cu(II), a low valency state is the lower of thecommonly occurring valencies, i.e. Fe(II) or Cu(I). Hence M in Formula Iis preferably Cu(I), Fe(II), Co(II), Ru(II) or Ni(II), most preferablyCu(I). Preferably, the coordinating ligand is (CH₃CN)₄. Y may be chosenfrom Cl, Br, F, I, NO₃, PF₆, BF₄, SO₄, CN, SPh, SCN, SePh or triflate(CF₃SO₃). Copper (I) triflate may be in the form of a commerciallyavailable benzene complex (CF₃SO₃Cu)₂C₆H₆. The most preferred compoundis CuBr. Preferably, the second component (b) is selected from

where R is independently selectable and is selected from straight,branched or cyclic alkyl, hydrogen, substituted alkyl, hydroxyalkyl,carboxyalkyl or substituted benzyl. Preferably the or each alkyl,hydroxyalkyl or carboxyalkyl contains 1 to 20, especially 1 to 5 carbonatoms.

X is a halide, especially I, Br, F or Cl.

The second component (b) may especially be selected from Formulae 13 to23:

where:

X=Br, I or Cl, preferably Br

R′=—H,

—(CH₂)_(p)R″ (where m is a whole number, preferably p=1 to 20, morepreferably 1 to 10, most preferably 1 to 5, R″=H, OH, COOH, halide, NH₂,SO₃, COX—where x is Br, I or C) or:

R¹¹¹=—COOH, —COX (where X is Br, I, F or Cl), —OH, —NH₂ or —SO₃H,especially 2-hydroxyethyl-2′-methyl-2′bromopropionate.

Especially preferred examples of Formula 16 are:

Br may be used instead at Cl in Formulae 16A and 16B.

The careful selection of functional alkyl halides allows the productionof terminally functionalized polymers. For example, the selection of ahydroxy containing alkyl bromide allows the production of α-hydroxyterminal polymers. This can be achieved without the need of protectinggroup chemistry.

Component (c) may be a 1,4-diaza-1,3-butadiene

a 2-pyridinecarbaldehyde imine

An Oxazolidone

or a Quinoline Carbaldehyde

where R₁, R₂, R₁₀, R₁₁, R₁₂ and R₁₃ may be varied independently and R₁,R₂, R₁₀, R₁₁, R₁₂ and R₁₃ may be H, straight chain, branched chain orcyclic saturated alkyl, hydroxyalkyl, carboxyalkyl, aryl (such as phenylor phenyl substituted where substitution is as described for R₄ to R₉),CH₂Ar (where Ar=aryl or substituted aryl) or a halogen. Preferably R₁,R₂, R₁₀, R₁₁, R₁₂ and R₁₃ may be a C₁ to C₂₀ alkyl, hydroxyalkyl orcarboxyalkyl, in particular C₁ to C₄ alkyl, especially methyl or ethyl,n-propylisopropyl, n-butyl, sec-butyl, tert butyl, cyclohexyl,2-ethylhexyl, octyl decyl or lauryl. R₁, R₂, R₁₀, R₁₁, R₁₂ and R₁₃ mayespecially be methyl.

R₃ to R₉ may independently be selected from the group described for R₁,R₂, R₁₀, R₁₁, R₁₂ and R₁₃ or additionally OCH_(2n+1) (where n is aninteger from 1 to 20), NO₂, CN or O═CR (where R=alkyl, benzyl PhCH₂ or asubstituted benzyl, preferably a C₁ to C₂₀ alkyl, especially a C₁ to C₄alkyl).

Furthermore, the compounds may exhibit a chiral centre α to one of thenitrogen groups. This allows the possibility for polymers havingdifferent stereochemistry structures to be produced.

Compounds of general Formula 25 may comprise one or more fused rings onthe pyridine group.

One or more adjacent R₁ and R₃, R₃ and R₄, R₄ and R₂, R₁₀ and R₉, R₈ andR₉, R₈ and R₇, R₇ and R₆, R₆ and R₅ groups may be C₅ to C₈ cycloalkyl,cycloalkenyl, polycycloalkyl, polycycloalkenyl or cyclicaryl, such ascyclohexyl, cyclohexenyl or norborneyl.

Preferred ligands include:

where: * indicates a chiral centre

R14 =Hydrogen, C₁ to C₁₀ branched chain alkyl, carboxy- or hydroxy- C₁to C₁₀ alkyl.

A second aspect of the invention provides a catalyst for additionpolymerization of olefinically unsaturated monomers, especially vinylicmonomers, comprising:

a first component of Formula 51

[ML_(m)]^(n+)A⁻

wherein M=a transitional metal in a low valency state;

L=an organodiimine, where at least one of the nitrogens of the diimineis not part of an aromatic ring,

A=an anion

n=a whole integer of 1 to 3

m=an integer of 1 to 2.

(e) An initiator comprising a homolytically cleavable bond with ahalogen atom, as previously defined.

Preferably, M is as previously defined for component (a). L may be acompound according to Formula 24, 25, 26 or 27, as previously defined. Amay be F, Cl, Br, I, NO₃, SO₄ or CuX₂ (where X is a halogen).

The preferred initiators (e) are as defined for the first aspect of theinvention. The invention also provides the use of the catalyst accordingto the first or second aspect of the invention in the additionpolymerization of one or more olefinically unsaturated monomers and thepolymerized products of such processes.

The components (a), (b) and (c), or (d) and (e) may be used together inany order.

The inventors have unexpectedly found that the catalyst will work at awide variety of temperatures, including room temperature and as low as−15° C. Accordingly, preferably the catalyst is used at a temperature of−20° C. to 200° C., especially −20° C. to 150° C., 20° C. to 13° C.,more preferably 90° C.

The olefinically unsaturated monomer may be a methacrylic, an acrylate,a styrene, methacrylonitrile or a diene such as butadiene.

Examples of olefinically unsaturated monomers that may be polymerizedinclude methyl methacrylate, ethyl methacrylate, propyl methacrylate(all isomers), butyl methacrylate (all isomers), and other alkylmethacrylates; corresponding acrylates; also functionalizedmethacrylates and acrylates including glycidyl methacrylate,trimethoxysilyl propyl methacrylate, allyl methacrylate, hydroxyethylmethacrylate, hydroxypropyl methacrylate, dialkylaminoalkylmethacrylates; fluoroalkyl (meth)acrylates; methacrylic acid, acrylicacid; fumaric acid (and esters), itaconic acid (and esters), maleicanhydride; styrene, α-methyl styrene; vinyl halides such as vinylchloride and vinyl fluoride; acrylonitrile, methacrylonitrile;vinylidene halides of formula CH₂═C(Hal)₂ where each halogen isindependently Cl or F; optionally substituted butadienes of the formulaCH₂═C(R₁₅) C(R₁₅)═CH₂ where R₁₅ is independently H, C1 to C10 alkyl, Cl,or F; sulphonic acids or derivatives thereof of formula CH₂═CHSO₂OMwherein M is Na, K, Li, N(R₁₆)₄ where each R₁₆ is independently H or Clor V10 alkyl, D is COZ, ON, N(R₁₆ )2 or SO₂OZ and Z is H, Li, Na, K orN(R₁₆)_(4;) acrylamide or derivatives thereof of formula CH₂═CHCON(R₁₆)₂and methacrylamide or derivative thereof of formula CH₂═C(CH₃)CON(R₁₆)₂.Mixtures of such monomers may be used.

Preferably, the monomers are commercially available and may comprise afree-radial inhibitor such as 2, 6-di-tert-butyl-4-methylphenol ormethoxyplenol.

Preferably, the co-catalysts are used in the ratios (c):(a) 0.01 to1000, preferably 0.1 to 10, and (a):(b) 0.0001 to 1000, preferably 0.1to 10, where the degree of polymerization is controlled by the ratio ofmonomer to (b).

Preferably, the components of the catalyst of the second aspect of theinvention are added at a ratio M:initiator of 3:1 to 1:100.

Preferably, the amount of diimine:metal used in the systems is between100:1 and 1:1, preferably 5:1 to 1:1, more preferably 3:1 to 1:1.

The reaction may take place with or without the presence of a solvent.Suitable solvents in which the catalyst, monomer and polymer product aresufficiently soluble for reactions to occur include water, protic andnon-protic solvents including propionitrile, hexane, heptane,dimethoxyethane, diethoxyethane, tetrahydrofuran, ethylacetate,diethylether, N,N-dimethylformamide, anisole, acetonitrile,diphenylether, methylisobutyrate, butan-2-one, toluene and xylene.Especially preferred solvents are xylene and toluene, preferably thesolvents are used at at least 1% by weight, more preferably at at least10% by weight.

Preferably, the concentration of monomer in the solvents is 100% to 1%,preferably 100% to 5%.

The reaction may be undertaken under an inert atmosphere such asnitrogen or argon.

The reaction may be carried out in suspension, emulsion, mini-emulsionor in a dispersion.

Statistical copolymers may be produced using the catalysts according tothe present invention. Such copolymers may use 2 or more monomers in arange of about 0-100% by weight of each of the monomers used.

Block copolymers may also be prepared by sequential addition of monomersto the reaction catalyst.

Telechelic polymers, may be produced using catalysts of the invention.For example, a functional initiator such as Formula 21 may be used withtransformation of the ωBr group to a functional group such as —OH or—CO₂H via use of a suitable reactant such as sodium azide.

Comb and graft copolymers may be produced using the catalysts of theinvention to allow, for example, polymers having functional side chainsto be produced, by use of suitable reagents.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments of the invention will now be described by way of example andwith reference to the following figures:

FIG. 1 shows the structure of the ligand 2,6 dimethylanilineDAB;

FIG. 2 shows the crystal structure of the cation obtained by reactingtBuDAB and CuBr together;

FIGS. 3 and 4 show Mn dependence on conversion of different monomerinitiator ratios for styrene and methylmethacrylate respectively;

FIG. 5 shows Mw/Mn dependence on conversion for bulk polymerization ofstyrene at 80° C.;

FIG. 6 shows kinetic plots for polymerization of methylmethacrylate at90° C.;

FIG. 7 shows the reaction scheme for the production of hydroxyterminally functionalized PMMA. (i) Br₂-P, (ii) Ethylene glycol, (iii)CuBr/3/MMA, (iv) benzoyl chloride;

FIG. 8 shows a selected region from ′H NMR spectra of (a) 3, (b) 4 (c)5;

FIG. 9 shows partial MALDI-TOF-MS of 3 between x=8 and 11, peakscorrespond to lithium adducts of molecular ions with no observablefragmentation;

FIG. 10 shows a plot showing how Mn from SEC increases with conversionfor experiments D-K.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS EXAMPLES Synthesis ofLigands

Diazabutadiene (DAB) Ligands

To a stirred solution of 40% aqueous glyoxal (0.25 mol) in a conicalflask was added the required amine dropwise (0.5 mol). After a period oftime a pale yellow solution formed which was taken up with water andfiltered. The resulting precipitate was dissolved in diethyl ether andpoured over a large excess of magnesium sulfate. The solution was leftfor twelve hours to remove all the water and the solution was filtered.Ether was removed on a rotary evaporator then the product recrystallizedfrom ether. TertButyl DAB (tBu DAB) and isoPropyl DAB (iPr DAB) weresimilarly manufactured using t-butylamine and isopropylaminerespectively as the starting amine. Such compounds are superior to2,2-bipyridine in accepting electron density

Pyridine Carbaldehyde Ligands

To a stirred solution of pyridine carbaldehyde in ether was added anequimolar quantity of amine. The solution was left for 3 hours thenpoured over an excess of magnesium sulfate. The solution was filteredand the ether removed on a rotary evaporator. Some ligands formed yellowoils and were purified by distillation under reduced pressure. Solidswere purified by recrystallization from ether.

tBu PCA, iPr PCA, nButyl PCA (nBu PCA), Dimethylaniline PCA,Diisopropylaniline PCA and methoxyaniline PCA were also made by reacting^(t)BuNH₂, ^(i)PrNH₂, ^(n)BuNH₂, 2,6-dimethylaniline,2,6-diisoproxylaniline and 4-methoxyaniline, respectively as the amine.

Characterization of Ligands

Ligands have been initially characterized by NMR and EI/CI massspectrometry. Mass spec data is tabulated below.

DIAZABUTIENE (DAB) LIGANDS

Structure RMM M/Z tBu DAB 168 166 iPr DAB 140 141 Dimethylaniline DAB262 249

PYRIDINE CARBALDEHYDE (PCA) LIGANDS

Structure RMM M/Z tBu PCA 162 163 iPr PCA 149 149 nBu PCA 162 163Aniline PCA 182 182 Dimethylaniline PCA 212 209 Diisopropylaniline PCA268 223 Methoxyaniline PCA 197 211

A crystal structure has been obtained of the ligand 2, 6 dimethylanilineDAB (FIG. 1). This shows a E configuration of double bonds which mustfold around the metal centre to form the catalyst.

Synthesis of Catalysts

To a solution of ligand (in acetone) in a schlenk ways added copperbromide, chloride or Cu(CH₃CN)₄BF₄ under nitrogen. The solution wasfiltered by cannular and placed in a freezer. Solvent was removed byfiltration and the crystals examined by FAB mass spectrometry. Catalystswere synthesised with equimolar quantities of ligand and anion or excessligand (2:1). Both experiments resulted in the detection of a peakcorresponding to CuL2.

L=ligand.

Mass spectometry data M/Z Ligand Ligand:anion Anion CuL CuL₂ Cu₂L₂ClCu₂L₂Cl₂ tBuDAB 1:1 Br 231 399 tBuDAB 1:1 BF₄ 231 399 tBuDAB 2:1 Br 231399 tBuDAB 1:1 Cl — 399 499 597 iPrDAB 1:1 Br 203 343 tBuPCA 1:1 Br 225387 tBuPCA 1:1 BF₄ 225 387 tBuPCA 1:1 Cl — 387 Bipy 1:1 Br 300 456 Bipy1:1 BF₄ 219 375 Bipy 2:1 BF₄ 219 375 Bipy 1:1 Cl — 375

Bipy (Bipyridyl) is included as a comparison.

A crystal structure has been obtained for the reaction of tBu DAB andCuBr indicating a tetrahedral intermediate (FIG. 2).

Polymer Synthesis

The catalysts were used to control the propagation of styrene andmethylmethacrylate.

All polymerizations were performed with excess ligand [L]:[Cu] 3:1 andthe catalyst is synthesized in situ.

General Method for Polymerization of Methylmethacrylate

To a Schlenk flask to be purged with nitrogen was added 0.54 mls ethyl2-bromo-isobutyrate (0.00372 mols) in 10 mls methylmethacrylate (0.0935mols). The desired ligand was then added (0.01122 mols) and the entiresolution was freeze pump thaw degassed. 0.536 g copper bromide (0.00374mols) was then added whilst stirring. When the solution turned deep redindicating formulation of the catalyst the Schlenk flask was immersed inan oil bath at 90° C.

Polymerization Results

All polymerisations are based on the following mole ratios.

Copper X=catalyst based on copper.

Styrene (Sty) was initiated with 1-phenylethyl bromide or chlorine.

Methylmethacrylate (MMA) was initiated with ethyl-2-bromo isobutyrate.

ligand mon. X t/hrs T/*C Mn Mw PDi Conv % tbuDAB STY Br 24 110 2,1734,438 2 11 iPrDAB STY Br 24 110 1,975 72,587 38 5 dimethylaniline DABSTY Br 24 110 467 4,156 9 80 tBuPCA STY Br 24 110 338 1,110 3.2 1aniline PCA STY Br 24 110 6,458 22,376 3.5 41 dimethylaniline STY Br 24110 3,017 9,167 3 68 tBuPCA STY Cl 20 130 42,551 102,776 2.45 20 nBuPCASTY Cl 3 130 6,951 22,571 3.25 40 iPrPCA STY Cl 20 130 15,607 41,1252.64 33 aniline PCA STY Br 20 110 6,458 22,376 4 41 dimethylaniline PCASTY Br 20 110 3,017 9,167 3 68 ipropylaniline PCA STY Br 20 130 3,70010,074 2.72 61 methoxyaniline PCA STY Br 20 130 9,723 24,772 2.5 69aniline PCA MMA Br 18 110 477 4,600 9.6 2 dimethylaniline PCA MMA Br 18110 6,293 12,210 1.94 68 nBuPCA MMA Br 4 100 10,251 12,273 1.2 95 nBuPCAMMA Br 1 130 7,376 12,422 1.68 — nBuPCA STY Br 40 80 5,492 7,313 1.33 43nBuPCA STY Br 20 80 6,343 9,533 1.5 39

Polymerization with tBuDAB

t-BuDAB was also investigated in more detail using different ratios ofLigand (L), Initiator (I) and catalyst (Cu).

Styrene at 100° C.

L:I Cu:I Mn PDI % Conv. 3 1 2173 2.0 11 3 20 2603 4.0 7 3 100 2169 5.8 81 1 2400 3.6 9 1 100 8042 14 7 3 1 2020 4.1 Low

This shows that PDI may be controlled by varying the ratio of L:I and/orCu:I.

Polymerizations with nBuPCA

A successful ligand was nBuPCA which will form the following copper (I)structure:

This catalyst has been used to obtain kinetic data for thepolymerization of both styrene and methylmethacrylate. Temperaturecontrol is important to prevent termination leading to tailing of theresulting MW distribution. If termination is prevented thenpolydispersity will decrease with time. Mn conversion plots have beenobtained at different monomer to initiator ratios.

FIGS. 3 and 4 show Mn dependence on conversion at differentmonomer:initiator for styrene and methylmethacrylate at 80° C.

FIG. 5 shows Mw/Mn dependence on conversion for bulk polymerization ofstyrene at 80° C.

FIG. 6 shows kinetic plots for the polymerization of methylmethacrylateat 90° C.

Synthesis of Block Co-polymers

This was investigated using methylmethacrylate, benzylmethacrylate(BzMA) and 2 hydroxyethylmethacrylate (HEMA) the results of which areshown in the table below:

TABLE B BLOCK ONE BLOCK TWO % Mon. Mn Mw PDi Mon. Mn Mw PDi MMA MMA2,469 2,965 1.2 MMA 5,599 7,337 1.31 100 MMA 2,469 2,965 1.2 BzMA 4,9086,500 1.32 70 MMA 2,499 3,431 1.37 BzMA 5,934 10,749 1.81 54 MMA 2,4993,431 1.37 HEMA 3,298 5,544 1.68 70

Statistical Copolymers

An example of a statistical copolymer was produced using a compound ofFormula 16B as initiator and a compound of Formula 45 as the ligand.

1 g of 2-hydroxyethyl methacrylate with 9.36g of MMA (I. e. 7.7. mole %)was polymerized with the following results:

Amount Solvent Amt. ligand/ (conc Amt. Initiator Temp. Time InitiatorLigand mL wt %) CuBr/g /g ° C. mins. 16B 45 0.37 33.3 0.13 0.16 90 2,760

Results: Mn PDI % HEMA (NMR) 14,764 1.21 4.5

Further Experimentation

Further experimentation was also carried out using ligands of Formula33.

This was synthesized as follows:

30 mls of diethylether was placed in a conical flask. 1.78 mls of2-pyridine carbaldehyde (2.00 g, 1.867×10⁻² moles) were added prior to1.54 mls or propylamine (1.11 g, 1.873×10⁻² moles). The reaction mixtureimmediately turns yellow. The mixture was stored for 10 minutes at roomtemperature prior to the addition of magnesium sulfate and stirring fora further 30 minutes. The reaction mixture was filtered and thevolatiles removed under reduced pressure. The product is isolated as ayellow oil.

Polymerization

0.688 g of copper (I) bromide (98% Aldrich)(4.796×10⁻⁴ moles) were addedto 10 mls of methylmethacrylate purified by passage down a columncontaining basic alumina and 3A sieves under nitrogen (9.349×10⁻² moles)in 20 mls of xylene (deoxygenated by 3 freeze-pump-thaw cycles and driedover 3A sieves for 12 hours). 0.2136 g of A (1.44×10⁻³ moles) were addedover 2 minutes with stirring at room temperature to give a homogenousdeep red/brown solution. 0.07mls of ethyl 2-bromoisobutyrate (0.0924 g,4.73×10⁻⁴ moles) were added and the reaction mixture heated to 90° C.for 485 minutes. Samples were taken at intervals and analyzed for Mn andconversion, see table. After 485 minutes poly(methylmethacrylate) wasisolated by precipitation into methanol in 78.6% yield with Mn=7020 andPDI (Mw/Mn)=1.27.

TIME % CONVERSION Mn PDI 120 16.47 2376 1.28 240 52.69 5249 1.22 30061.02 6232 1.18 360 67.56 6742 1.21 485 78.56 7020 1.27

The Production of α-hydroxy terminally functionalized PMMA

The initiator, ethyl-2-bromoisobutyrate was replaced with hydroxycontaining alkyl bromide so as to produce -hydroxy terminallyfunctionalized PMMA without the need to employ protecting groupchemistry.

Ligands of Formula 33 were used in the polymerization process.

2-hydroxyethyl-2′-methyl-2′bromopropionate was prepared as shown in FIG.7.

The conditions used in steps (1) and (ii) was as follows:

0.25 g of red phosphorous (8.06×10⁻³ mol) were added to 35.4 ml (0.338mol) of isobutyryl chloride. The mixture was placed under gentle refluxand 20ml of bromine (0.338 mol) were added slowly over 8 hours. Themixture was refluxed for a further 4 hours and the crude reactionmixture added slowly to 350 ml of anhydrous ethylene glycol (6.27 mol).The reaction mixture was refluxed for 4 hours, filtered into 500 ml ofdistilled water and the product extracted into chloroform. After washingwith water and sodium hydrogen carbonate and drying over magnesiumsulfate the product was isolated as a colorless liquid after the removalof solvent and vacuum distillation at 64.5° C. and 0.1 Torr. ′H NMR(CDCl₃, 373 K, 250.13 MHz) δ=4.30 (t, J 9.6 Hz, 2H), 3.85 (t, J 9.6 Hz,2H) 1.94 s, 6H), ₁₃C (′H) NMR (CDCl₃, 373 K, 100.6 mHz) δ=171.83, 67.30,60.70, 55.72, 30.59, IR (NaCl, film) 3436 (Br), 2977, 1736 (s), 1464,1391, 1372, 1278, 1168, 1112, 1080, 1023, 950, 644, E1 MS: 213, 211(mass peaks), 169, 167, 151, 149, 123, 121. The typical polymerizationprocedure used (steps iii and iv) was as follows:

0.1376 of copper(1)bromide (98%, 9.6×10⁻⁴ mol) were added to 40 ml ofxylene and 20 ml of methyl methacrylate (0.187 mol). 0.4272 g of 2(2.89×10⁻³ mol) were added and the mixture deoxygenated by onefreeze-pump-thaw cycle prior to the addition of 0.2029 g of 3(9.61×10⁻⁴) mol at room temperature. The deep red solution was heated at90° C. for 70 minutes. The final product was isolated by precipitationinto hexanes.

Atom transfer radical polymerization of MMA. using 3 as initiator inconjunction with 2 and CuBr was carried out at 90° C. in xylene[MMA]:[3]=20:1, [ligand]:[CuBr]:[3]=3:1:1 to give PMMA of structure 4.Polymerization was stopped at low conversion, 7.65%, after 70 minutes,so as to reduce the amount of termination by radical-radical reactions,reaction A. ′H NMR data (FIG. 8), clearly shows the presence of thehydroxyethyl ester group, originating from 2 and the methoxy to thebromo group at the propagating end at δ4.28, 3.82 and 3.74 respectively.The number average molecular mass, Mn, can be calculated directly fromNMR which gives a value of 2,430 which compares excellently with thatobtained from size exclusion chromatography against PMMA standards of2,320, PDI=1.12 (when precipitated into hexanes Mn−2960, PDI=1.12). Thisexcellent agreement indicates that the product has structure 4. This isconfirmed by matrix-assisted laser desorption-ionization time of flightmass spectrometry, FIG. 9. We see one series of peaks in theMALDI-TOF-MS indicating only one predominant structure i.e. 4. Forexample, the peaks at m/z 1319.0 and 1419.2 correspond to lithiumadducts of 4 where x=10 and 11 respectively, calculated m/z 1318.3 and1418.4. The narrow PDI of 4 is indicative ofk(propagation)>k(termination) i.e. pseudo living polymerization. Controlover Mn and PDI is obviously not affected detrimentally by the presenceof primary alcohol group present in the initiator, which might have beenexpected to complicate the reaction by coordination to the coppercatalyst. Indeed the PDI is narrower and the rate of polymerizationfaster with 3 than that obtained using a non-functional initiator. Thisis currently under investigation. Thus, controlled polymerization withthe copper complex as catalyst can be used to give PMMA or structure 4as the only detectable product under these conditions. The hydroxy groupcan be further reacted with benzoyl chloride to give 5 quantitatively.

The terminal benzoyl group of 5 is observed by ′H NMR, FIG. 8(c) and isdetected by SEC with UV detection at 200 nm, 4 shows no absorption atthis wavelength. MALDI TOF shows a new series of peaks corresponding to5 e.g. peaks are now observed at m/z 1423.0 and 1522.8 for x=10 and 11,calculated m/z 1422.3 and 1522.4; this reaction is quantitative and nopeaks from residual 4 are observed. When the reaction is carried out ata higher [MMA]:[3] ratio for 120 minutes a higher molecular weightpolymer is produced, Mn=4540, PDI=1.22, as expected, reactions B and C.Again analysis shows terminal hydroxy functionally.

Living or pseudo living polymerizations have a low rate of terminationrelative to rate of propagation. This is demonstrated by following areaction with time, reactions D-K; L is the final product from thisreaction. FIG. 10 shows that Mn increases linearly with conversion, upto approx. 80%, whilst PDI remains narrow for reaction with[MMA]:[3}−200. In this case the expected Mn (theory) at 100%conversion=[100/1×100.14 (mass of MMA)]+220 (mass of end groups)=20248.The PDI is broader than would be expected for a true livingpolymerization with fast initiation (theoretically 1+1/DP). However, PDIdoes not increase with increasing conversion as would be expected for areaction with significant termination and this is most probably due toslow initiation relative to propagation. ₁₂

In summary, atom transfer polymerization with the copper complex ascatalyst and 3 as initiator leads to hydroxy functional PMMA. Thepresence of the hydroxy group during the polymerization does not reducethe control over the polymerization, and a narrow PDI polymer withcontrolled Mn is obtained. The reaction shows all the characteristics ofa living/pseudo living polymerization. The structure of the product hasbeen confirmed by MALDI-TOF-MS and NMR spectrometry. Furthermore thehydroxy functionality can be further functionalized by reaction withacid chlorides in a quantitative reaction.

Conver- [3]/ [MMA]/ sion PDI Reaction^(d) 10⁴ mol mol t/min (%)^(d) MnSEC SEC A^(b) 9.61 0.187  70 —  2530 1.10 B^(c) 9.72 0.047 120 — 4540^(e) 1.22e C^(c) 9.72 0.047 120 —  3130 1.22 D^(b) 9.61 0.187  60 0.21  — — E^(b) 9.61 0.187 120  2.27  — — F^(b) 9.61 0.187 180 15.74 4980 1.21 G^(b) 9.61 0.187 240 48.20 12330 1.26 H^(b) 9.61 0.187 30059.75 15580 1.29 I^(b) 9.61 0.187 360 66.18 17920 1.27 J^(b) 9.61 0.187420 72.11 19500 1.27 K^(b) 9.61 0.187 480 75.05 20100 1.28 L^(b) 9.610.187 480 — 19427^(e) 1.31^(e) ^(a)All reactions carried out with[2]:[CuBr]:[3] = 3:1:1. ^(b)20 ml MMA in 40 ml xylene, ^(c)5 mls MMA in6 ml xylene. ^(d)From gravimetry. ^(e)After precipitation, otherwise astaken from reaction flask.

Further Examples of Initiators and Ligands

In order to demonstrate the effectiveness of the catalysts across therange of compounds chained, further experimentation was carried out.

Typical Polymerization Procedure

Methyl methacrylate (Aldrich) and xylene (AR grade, Fischer Scientific)were purged with nitrogen for 2 hours prior to use. The initiator,ethyl-2-bromoisobutyrate (98% Aldrich), and CuBr (99.999%, Aldrich) wereused as obtained and 2-pyridinal ^(n−)alkylimines were prepared asabove. A typical reaction method follows. CuBr (0.134 g,[Cu]:[Initiator]=1:1) was placed in a pre-dried Schlenk flask which wasevacuated and then flushed with nitrogen three times. Methylmethacrylate (10 ml) followed by 2-pyridinal ^(n−)alkylimine([ligand]:[Cu]=2:1) was added with stirring and, within a few seconds, adeep, brown solution formed. Xylene (20 ml) and, if appropriate,inhibitor were then added and the flask heated in a thermostatcontrolled oil bath to 90° C. When the solution had equilibratedethyl-2-bromoisobutyrate (0.14 ml, [Monomer]:[Initiator]=100:1) wasadded. Samples were taken by pipette at certain times or the reactionfollowed by automated dilatometry. This apparatus consists of a glasscapillary tube that is set on top of a reaction vessel. The vessel ischarged with a complete reaction mixture that has been freeze-pump-thawdegassed to ensure no dissolved gases are released into the capillary.After the vessel is fitted, the capillary is filled with degassedsolvent and the reaction mixture heated to the required temperature.During polymerization monomer is converted to polymer with a decrease inthe volume of the mixture. This decrease in volume can be followed bywatching the meniscus fall in the capillary, a process done in this caseby an electronic eye controlled by a computer program.

Characterization of Polymers

Monomer conversion was calculated by gravimetry and/or ¹H NMR and themolecular weights and molecular weight distributions (polydispersities)found by get permeation chromatography using tetrahydrofuran as eluentand the following columns (Polymer Laboratories): 5 μm guard and mixed-E(3000×7.5 mm), calibrated with PL narrow molecular weight poly(methylmethacrylate) standards with differential refractive index detectionand/or UV.

Solvent Amt. Initiator Ligand Amount (conc Amt. Initiator/ Temp. TimeExp. Formula Formula ligand/g wt %) CuBr mL ° C. mins.  1 15 28 0.375 500.134 0.181 90 210  2 15 28 0.375 50 0.134 0.181 90 360  3 15 29 0.37100 0.134 0.156 40 1440  4 15 33 0.273 33.3 0.134 0.137 90 240  5 15 400.273 33.3 0.134 0.137 90 1200  6 15 39 0.273 33.3 0.134 0.137 90 1320 7 15 44 0.25 33.3 0.134 0.137 90 2580  8 15 46 0.600 33.3 0.134 0.13790 2580  9 15 32 0.610 33.3 0.134 0.137 90 300 10 15 49 0.423 33.3 0.1340.137 90 1200 11 15 29 0.494 33.3 0.134 0.137 88 290 12 15 29 0.494 33.30.134 0.137 88 1260 13 15 31 0.536 33.3 0.134 0.137 90 1137 14 15 410.590 50 0.134 0.130 90 120 15 15 42 0.590 50 0.134 0.130 90 120 16 1541 0.590 50 0.134 0.130 90 240 17 15 47 0.42 50 0.13 0.14 40 1050 18 1547 0.42 50 0.13 0.14 40 2505 19 15 34 0.358 36 0.134 0.137 90 150 20 1535 0.386 36 0.134 0.137 90 150 21 15 36 0.414 36 0.134 0.137 90 150 2215 37 0.442 36 0.134 0.137 90 150 23 15 38 0.70 36 0.134 0.137 90 150 2421 28 0.37 33.3 0.13 0.16 90 300 25 21 33 0.41 50 0.13 0.16 90 120 26 2233 0.41 33.3 0.13 0.52 90 240 27 21 33 0.41 33.3 0.13 0.08 90 240 28 2133 0.41 33.3 0.13 0.05 90 240 29 21 32 0.37 100 0.134 0.156 40 1440 3021 32 0.37 33.3 0.134 0.156 90 300 31 23 29 0.37 33.3 0.134 0.178 90 27032 23 29 0.37 33.3 0.134 0.178 90 1320 33 16B 29 0.37 33.3 0.134 0.19390 1320 34 16B 45 0.45 g 50 0.13 0.19 90 2760 35 23 45 0.45 g 50 0.130.19 90 2760 36 16B 29 0.185 33.3* 0.067 0.096 90 2880 *25 mL of MMA

Exp. Mn PDI % Conversion  1 10818 1.28 100  2 5060 1.34 13.5  3 123101.70 91.6  4 9198 1.19 66  5 8717 1.49 87  6 31666 1.65 49  7 9054 2.712  8 5250 1.63 2  9 21318 1.78 86 10 53395 1.72 39 11 8990 1.16 55.6 1215147 1.26 97.6 13 8710 1.36 47.1 14 4300 1.45 5 15 4700 1.65 10 16 62001.45 28 17 6577 1.27 47 18 11216 1.23 75 19 6500 1.18 60.0 20 7400 1.2068.3 21 7320 1.20 72.1 22 7580 1.20 73.4 23 7900 1.23 73.4 24 11710 1.3025 28314 1.19 26 7700 1.14 27 28330 1.15 68.5 28 36380 1.17 50.6 2923780 1.07 38.5 30 26640 1.17 52.52 31 2177 1.10 2135 (by NMR) 32 10001.11 3.8 33 1900 1.08 20.3 34 11009 1.08 35 10200 1.13 36 23700 1.13

What is claimed is:
 1. A catalyst for addition polymerization ofolefinically unsaturated monomers comprising: a) a first compound MYwherein M is a transition metal in a low valency state or a transitionmetal in a low valency state coordinated to at least one coordinatingnon-charged ligand; and Y is a monovalent, divalent or polyvalentcounterion; b) an initiator compound comprising a homolyticallycleavable bond with a halogen atom; and c) an organodiimine, wherein atleast one of the nitrogens of the diimine is not part of an aromaticring.
 2. A catalyst according to claim 1 wherein the organodiimine isselected from the group consisting of: a 1,4-diaza-1,3-butadiene

a 2-pyridine carbaldehyde imine

an oxazolidone

 or a quinoline carbaldehyde

wherein R₁, R₂, R₁₀, R₁₁, R₁₂, and R₁₃ are independently selectable andmay be selected from the group consisting of H, straight chain, branchedchain or cyclic saturated alkyl, hydroxyalkyl, carboxyalkyl, aryl,CH₂Ar, wherein Ar is aryl or substituted, or a halogen; R₃ to R₉ areindependently selectable and may be selected from the group consistingof H, straight chain, branched chain or cyclic alkyl, hydroxyalkyl,carboxyalkyl, aryl CH₂ Ar, a halogen, OCH_(2n+I,) wherein n is aninteger of 1 to 20, NO₂, CN, O═CR wherein R=alkyl, aryl, substitutedaryl, benzyl PhCH₂ or a substituted benzyl.
 3. A catalyst according toclaim 2 wherein R₁ to R₁₃ are selected from the group consisting of C₁to C₂₀ alkyl, C₁ to C₂₀ hydroxyalkyl, C₁ to C₂₀ carboxyalkyl,n-propylisopropyl, n-butyl, sec-butyl, tert-butyl, cyclohexyl,2-ethylhexyl, octyldecyl and lauryl.
 4. A catalyst according to claim 2,wherein the organodiimine comprises a chiral center.
 5. A catalystaccording to claim 2 wherein one or more adjacent R₁ and R₃, R₃ and R₄,R₄ and R₂, R₁₀ and R₉, R₈ and R₉, R₈ and R₇, R₇ and R₆, R₆ and R₅ groupsare selected from the group consisting of alkyl, cycloalkenyl,polycycloalkyl, polycycloalkenyl and cyclicaryl, containing 5 to 8carbon atoms.
 6. A catalyst according claim 1 wherein M is selected fromthe group consisting of Cu(I), Fe(II), Co(II), Ru(II), Ni(II) Sm(II),Ag(I) and Yb(II).
 7. A catalyst according claim 1, wherein Y is selectedfrom the group consisting of Cl, Br, I, NO₃, PF₆, BF₄, SO₄ and CF₃ SO₃,CN, SPh, ScN and SePh.
 8. A catalyst according to claim 1, wherein theinitiator is selected from the group consisting of: RX  Formula 2,

wherein R is independently selectable and is selected from the groupconsisting of straight chain alkyl, branched chain alkyl, cyclic alkyl,hydrogen, substituted alkyl, hydroxyalkyl, carboxyalkyl, aryl andsubstituted aryl and substituted benzyl, and wherein X=a halide.
 9. Acatalyst according to claim 8, wherein the initiator is

wherein: X=Br, I or Cl, r R′=—H, —(CH₂)_(p)R″, wherein p is a wholenumber and R″=H, OH, NH₂, SO₃H, COOH, halide, COX, where X is Br, I orCl, or

 R¹¹¹=—COOH, —COX, where X is Br, I or Cl, , —OH, —NH₂ or —SO₃H.
 10. Acatalyst according to claim 9 wherein b is2-hydroxyethyl-2′bromopropionate.
 11. A method for additionpolymerization of one or more olefinically saturated monomerscomprising: addition polymerizing one or more olefinically saturatedmonomers using the catalyst of claim
 1. 12. The method according toclaim 11, wherein the addition polymerization is conducted at atemperature between −20° C. to 200° C.
 13. The method according to claim12, wherein the addition polymerization is conducted at a temperaturebetween 20° C. and 130° C.
 14. The method according to claim 11, whereinthe olefinically saturated monomers are selected from methylmethacrylate, ethyl methacrylate, propyl methacrylate including allisomers thereof, butyl methacrylate including all isomers thereof, otheralkyl methacrylates, corresponding acrylates, functionalizedmethacrylates and acrylates fluoroalkyl (meth)acrylates, methacrylicacid, acrylic acid, fumaric acid and esters thereof, itaconic acid andesters thereof, nucleic anhydride, styrene, α-methyl styrene, vinylhalides, acrylonitrile, methacrylonitrile, vinylidene halides of formulaCH₂—C(Hal)₂ wherein each halogen is independently Cl or F, optionallysubstituted butadiene of the formula CH₂═C(R₁₅)C(R₁₅)═CH₂ wherein R₁₅ isindependently H, Cl to C10 alkyl, Cl or F, sulphonic acids orderivatives thereof of formula CH₂═CHSO₂OM wherein M is NaS, K, Li,NR₁₆)₄, or —(CH₂)₂—D wherein each R₁₆ is independently H or Cl or C10alkyl, D is CO₂Z, OH, NR₁₆)₂ or SO₂OZ and Z is H. Li, Na, K or NR₁₆)₄,acrylamide or derivatives thereof of formula CH₂—C(CH₃)CON(R₁₆)₂, andwherein mixtures thereof.
 15. The method according to claim 11, whereinthe polymerization is conducted in water, a protic solvent or anonprotic solvent.
 16. A method for producing a statistical copolymer, ablock polymer, a telechelic polymer or a comb and graft copolymer ofmonomers, the method comprising: producing at least one of a statisticalcopolymer, a block polymer, a telechelic polymer and a comb and graftcopolymer of monomers using the catalyst of claim
 1. 17. A catalyst foraddition polymerization of olefinically unsaturated monomers comprising:(a) a first component of formula (ML_(m))^(n+)A^(n−) wherein M=atransition metal of low valency state; L=an organodiimine where at leastone of the nitrogens of the diimine is not part of an aromatic ring;A=an anion; n=an integer from 1 to 3; m=and integer from 1 to 2; and (b)an initiator compound comprising a homolytically cleavable bond with ahalogen atom.
 18. A catalyst according to claim 17, wherein A isselected from the group consisting of Cl, Br, F, I, NO₃, SO₄ and CuX₂,wherein X is a halogen.